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A high-resolution oceanic section of dissolved iron stable isotope ratios reveals that the primary source of dissolved iron to the North Atlantic is atmospheric dust, while seafloor sediments and submarine volcanic vents also contribute significantly. Iron sources in the North Atlantic Ocean Iron availability limits phytoplankton growth throughout the oceans, acting as a key influence on the global carbon cycle and the oceanic response to changing climate. But large uncertainties remain as to the relative importance of the various sources of iron, including windblown dust and hydrothermal vents. This paper presents a high-resolution transect of seawater dissolved stable iron isotope ratios and iron concentrations in the North Atlantic Ocean. Saharan dust aerosol emerges as the dominant source of dissolved iron along the section, with sediments and hydrothermal vents also significant. Changes in these sources through time may have wide-ranging implications for the global carbon cycle. Dissolved iron is an essential micronutrient for marine phytoplankton, and its availability controls patterns of primary productivity and carbon cycling throughout the oceans 1 , 2 . The relative importance of different sources of iron to the oceans is not well known, however, and flux estimates from atmospheric dust, hydrothermal vents and oceanic sediments vary by orders of magnitude. Here we present a high-resolution transect of dissolved stable iron isotope ratios (δ 56 Fe) and iron concentrations ([Fe]) along a section of the North Atlantic Ocean. The different iron sources can be identified by their unique δ 56 Fe signatures, which persist throughout the water column. This allows us to calculate the relative contribution from dust, hydrothermal venting and reductive and non-reductive sedimentary release to the dissolved phase. We find that Saharan dust aerosol is the dominant source of dissolved iron along the section, contributing 71–87 per cent of dissolved iron. Additional sources of iron are non-reductive release from oxygenated sediments on the North American margin (10–19 per cent), reductive sedimentary dissolution on the African margin (1–4 per cent) and hydrothermal venting at the Mid-Atlantic Ridge (2–6 per cent). Our data also indicate that hydrothermal vents in the North Atlantic are a source of isotopically light iron, which travels thousands of kilometres from vent sites, potentially influencing surface productivity. Changes in the relative importance of the different iron sources through time may affect interactions between the carbon cycle and climate.

Atmospheric dust is an important source of the micronutrient Fe to the oceans. Although relatively insoluble mineral Fe is assumed to be the most important component of dust, a relatively small yet highly soluble anthropogenic component may also be significant. However, quantifying the importance of anthropogenic Fe to the global oceans requires a tracer which can be used to identify and constrain anthropogenic aerosols in situ. Here, we present Fe isotope (δ 56 Fe) data from North Atlantic aerosol samples from the GEOTRACES GA03 section. While soluble aerosol samples collected near the Sahara have near-crustal δ 56 Fe, soluble aerosols from near North America and Europe instead have remarkably fractionated δ 56 Fe values (as light as −1.6‰). Here, we use these observations to fingerprint anthropogenic combustion sources, and to refine aerosol deposition modeling. We show that soluble anthropogenic aerosol Fe flux to the global surface oceans is highly likely to be underestimated, even in the dusty North Atlantic. The relative importance of crustal vs. anthropogenic dust deposition for iron cycling in the surface ocean is unclear. Based on analysis of iron isotope data from North Atlantic aerosol samples, the authors can reveal the relative importance of anthropogenic iron emissions and its impact on marine biogeochemistry.

Dissolution of marine sediment is a key source of dissolved iron (Fe) that regulates the ocean carbon cycle. Currently, our prevailing understanding, encapsulated in ocean models, focuses on low-oxygen reductive supply mechanisms and neglects the emerging evidence from iron isotopes in seawater and sediment porewaters for additional nonreductive dissolution processes. Here, we combine measurements of Fe colloids and dissolved δ56Fe in shallow porewaters spanning the full depth of the South Atlantic Ocean to demonstrate that it is lithogenic colloid production that fuels sedimentary iron supply away from low-oxygen systems. Iron colloids are ubiquitous in these oxic ocean sediment porewaters and account for the lithogenic isotope signature of dissolved Fe (δ56Fe = +0.07 ± 0.07‰) within and between ocean basins. Isotope model experiments demonstrate that only lithogenic weathering in both oxic and nitrogenous zones, rather than precipitation or ligand complexation of reduced Fe species, can account for the production of these porewater Fe colloids. The broader covariance between colloidal Fe and organic carbon (OC) abundance suggests that sorption of OC may control the nanoscale stability of Fe minerals by inhibiting the loss of Fe(oxyhydr)oxides to more crystalline minerals in the sediment. Oxic ocean sediments can therefore generate a large exchangeable reservoir of organo-mineral Fe colloids at the sediment water interface (a “rusty source”) that dominates the benthic supply of dissolved Fe to the ocean interior, alongside reductive supply pathways from shallower continental margins.

Cadmium (Cd) is a micronutrient and a tracer of biological productivity and circulation in the ocean. The correlation between dissolved Cd and the major algal nutrients in seawater has led to the use of Cd preserved in microfossils to constrain past ocean nutrient distributions. However, linking Cd to marine biological processes requires constraints on marine sources and sinks of Cd. Here, we show a decoupling between Cd and major nutrients within oxygen-deficient zones (ODZs) in both the Northeast Pacific and North Atlantic Oceans, which we attribute to Cd sulfide (CdS) precipitation in euxinic microenvironments around sinking biological particles. We find that dissolved Cd correlates well with dissolved phosphate in oxygenated waters, but is depleted compared with phosphate in ODZs. Additionally, suspended particles from the North Atlantic show high Cd content and light Cd stable isotope ratios within the ODZ, indicative of CdS precipitation. Globally, we calculate that CdS precipitation in ODZs is an important, and to our knowledge a previously undocumented marine sink of Cd. Our results suggest that water column oxygen depletion has a substantial impact on Cd biogeochemical cycling, impacting the global relationship between Cd and major nutrients and suggesting that Cd may be a previously unidentified tracer for water column oxygen deficiency on geological timescales. Similar depletions of copper and zinc in the Northeast Pacific indicate that sulfide precipitation in ODZs may also have an influence on the global distribution of other trace metals.

Oceanic iron inputs must be traced and quantified to learn how they affect primary productivity and climate. Chemical reduction of iron in continental margin sediments provides a substantial dissolved flux to the oceans, which is isotopically lighter than the crust, and so may be distinguished in seawater from other sources, such as wind-blown dust. However, heavy iron isotopes measured in seawater have recently led to the proposition of another source of dissolved iron from ‘non-reductive’ dissolution of continental margins. Here we present the first pore water iron isotope data from a passive-tectonic and semi-arid ocean margin (South Africa), which reveals a smaller and isotopically heavier flux of dissolved iron to seawater than active-tectonic and dysoxic continental margins. These data provide in situ evidence of non-reductive iron dissolution from a continental margin, and further show that geological and hydro-climatic factors may affect the amount and isotopic composition of iron entering the ocean. The dissolution of iron from sediments along ocean margins may stimulate photosynthesis and moderate global climate. This study shows how margin sediments supply iron in varying amounts between regions, and by distinct mechanisms, which may be due to geological characteristics and hydrological controls on land.

Substantial amounts of nitrogen fixation occur in the North Atlantic subtropical gyre, due to the activity of cyanobacteria with high iron requirements. Iron is delivered to this region by dust from the Sahara Desert. However, this dust deposition is typically localized and episodic. Therefore, other sources of iron may also be important. Here, we report observations of dissolved iron concentrations in a Gulf Stream cold-core ring, which transported iron-rich water from near the continental slope into the subtropical gyre. We find that iron concentrations were elevated in the ring compared with subtropical waters, reflecting its source waters. Using iron data from these source waters and the identification of ring activity in satellite data, we estimate that cold-core rings provide a net flux of 0.3 ± 0.17 × 108 mol Fe yr−1 across the northwestern gyre edge, on the order of 15% of our median estimates of gyre-wide supply of iron by dust deposition. We suggest that iron supply from cold-core rings is an important source of iron to the northwestern gyre edge. We conclude that mesoscale ocean circulation features may play an important role in subtropical nutrient and carbon cycling.

The authors thank Captain Schwarze and the crew of the RV Polarstern (GN05 cruise); chief scientist Torsten Kanzow (AWI); Nicola Herzberg and Jaw Chuen Yong (GEOMAR) for assistance with sample collection; Takamasa Tsubouchi (AWI), Eike Köhn (GEOMAR) and Nat Wilson (Woods Hole Oceanographic Institution) for CTD handling; Gerd Rohardt (AWI) for CTD data processing; Christian Schlosser and Shao-Min Chen (GEOMAR) for assistance during trace element analyses; Martin Graeve and KaiUwe Ludwichowski (AWI) for macronutrient analysis; and Hanno Meyer (AWI) for the analyses of oxygen isotopes. S.K. was financed by GEOMAR and the German Research Foundation (DFG award number AC 217/1-1 to E.A.). M.H. received support from the DFG (award number HO 6321/1-1) and the GLACE project, organized by the Swiss Polar Institute and supported by the Swiss Polar Foundation. J.S. acknowledges support from the German Federal Ministry of Education and Research (BMBF) within the GROCE project (grant 03F0778A).

Recent recession of the Larsen Ice Shelf C has revealed microbial alterations of illite in marine sediments, a process typically thought to occur during low-grade metamorphism. In situ breakdown of illite provides a previously-unobserved pathway for the release of dissolved Fe 2+ to porewaters, thus enhancing clay-rich Antarctic sub-ice shelf sediments as an important source of Fe to Fe-limited surface Southern Ocean waters during ice shelf retreat after the Last Glacial Maximum. When sediments are underneath the ice shelf, Fe 2+ from microbial reductive dissolution of illite/Fe-oxides may be exported to the water column. However, the initiation of an oxygenated, bioturbated sediment under receding ice shelves may oxidize Fe within surface porewaters, decreasing dissolved Fe 2+ export to the ocean. Thus, we identify another ice-sheet feedback intimately tied to iron biogeochemistry during climate transitions. Further constraints on the geographical extent of this process will impact our understanding of iron-carbon feedbacks during major deglaciations. Recent recession of the Larsen Ice Shelf C has revealed that microbial alteration of illite can occur within marine sediments, a process previously thought to only occur abiotically during low-grade metamorphism. Here, the authors show that such microbial alteration of illite could provide a potential source of Fe release to Southern Ocean waters during Holocene glacial cycles.

The stoichiometry of biological components and their influence on dissolved distributions have long been of interest in the study of the oceans. Cobalt has the smallest oceanic inventory of inorganic micronutrients and hence is particularly vulnerable to influence by internal oceanic processes including euphotic zone uptake, remineralization, and scavenging. Here we observe not only large variations in dCo : P stoichiometry but also the acceleration of those dCo : P ratios in the upper water column in response to several environmental processes. The ecological stoichiometry of total dissolved cobalt (dCo) was examined using data from a US North Atlantic GEOTRACES transect and from a zonal South Atlantic GEOTRACES-compliant transect (GA03/3_e and GAc01) by Redfieldian analysis of its statistical relationships with the macronutrient phosphate. Trends in the dissolved cobalt to phosphate (dCo : P) stoichiometric relationships were evident in the basin-scale vertical structure of cobalt, with positive dCo : P slopes in the euphotic zone and negative slopes found in the ocean interior and in coastal environments. The euphotic positive slopes were often found to accelerate towards the surface and this was interpreted as being due to the combined influence of depleted phosphate, phosphorus-sparing (conserving) mechanisms, increased alkaline phosphatase metalloenzyme production (a zinc or perhaps cobalt enzyme), and biochemical substitution of Co for depleted Zn. Consistent with this, dissolved Zn (dZn) was found to be drawn down to only 2-fold more than dCo, despite being more than 18-fold more abundant in the ocean interior. Particulate cobalt concentrations increased in abundance from the base of the euphotic zone to become  ∼  10 % of the overall cobalt inventory in the upper euphotic zone with high stoichiometric values of  ∼  400 µmol Co mol−1 P. Metaproteomic results from the Bermuda Atlantic Time-series Study (BATS) station found cyanobacterial isoforms of the alkaline phosphatase enzyme to be prevalent in the upper water column, as well as a sulfolipid biosynthesis protein indicative of P sparing. The negative dCo : P relationships in the ocean interior became increasingly vertical with depth, and were consistent with the sum of scavenging and remineralization processes (as shown by their dCo : P vector sums). Attenuation of the remineralization with depth resulted in the increasingly vertical dCo : P relationships. Analysis of particulate Co with particulate Mn and particulate phosphate also showed positive linear relationships below the euphotic zone, consistent with the presence and increased relative influence of Mn oxide particles involved in scavenging. Visualization of dCo : P slopes across an ocean section revealed hotspots of scavenging and remineralization, such as at the hydrothermal vents and below the oxygen minimum zone (OMZ) region, respectively, while that of an estimate of Co* illustrated stoichiometrically depleted values in the mesopelagic and deep ocean due to scavenging. This study provides insights into the coupling between the dissolved and particulate phase that ultimately creates Redfield stoichiometric ratios, demonstrating that the coupling is not an instantaneous process and is influenced by the element inventory and rate of exchange between phases. Cobalt's small water column inventory and the influence of external factors on its biotic stoichiometry can erode its limited inertia and result in an acceleration of the dissolved stoichiometry towards that of the particulate phase in the upper euphotic zone. As human use of cobalt grows exponentially with widespread adoption of lithium ion batteries, there is a potential to affect the limited biogeochemical inertia of cobalt and its resultant ecology in the oceanic euphotic zone.

Dissolved iron (dFe) is an essential micronutrient for phytoplankton, with vanishingly low oceanic dissolved concentrations (pico- to nanomoles per kg) known to limit growth—and thus influence primary productivity and carbon cycling—over much of the surface ocean. However, because of the considerable challenges associated with contamination-free sample collection and accurate analysis of such low dFe concentrations, the first reliable dFe measurements came only in the 1980s. Further, by 2003, despite several decades of research, there were only ~25 full-depth oceanic dFe profiles worldwide, with dust considered to be the main oceanic dFe source. Since 2008, facilitated by the extensive field campaign and rigorous intercalibration of the international GEOTRACES program, there has been an “explosion” in the availability of oceanic dFe data, with hundreds of profiles now available. Concurrently, there has been a paradigm shift to a view of the marine Fe cycle where multiple sources contribute, and some forms of dFe can be transported great distances through the intermediate and deep ocean. Here, we showcase the GEOTRACES dFe datasets across the different ocean basins, synthesize our current multi-source view of the oceanic Fe cycle, spotlight sediments as an important dFe source, and look to future directions for constraining oceanic dFe boundary exchange.